Aromatic di-functional phosphorus esters



3,014,950 AROMATIC DI-FUNCTIONAL PHOSPHORUS ESTERS Gail H. Birum,Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo., acorporation of Delaware No Drawing. Filed Dec. 15, 1958, Ser. No.780,224 8 Claims. (Cl. 260-461) The present invention relates to organiccompounds of phosphorus and more particularly provides a new andvaluable class of aromatic di-functional phosphorus esters and themethod of preparing the same.

According to the invention, there are provided aromatic phosphites orthiophosphites or aromatic phosphonites of esters of hydroxy phosphonicacids by the reaction of an aromatic trivalent phosphorus chloride withan aldehyde and a triorgano phosphite substantially according to thescheme wherein R and R are selected from the class consisting of (1)aromatic hydrocarbons which are free of olefini and acetylenicunsaturation and which contain from 6' to 12 carbon atoms and (2) saidaromatic hydrocarbons carrying halogen substitution, X is selected fromthe: class consisting of -O- and S, nis an integer} of to 1, Z isselected from the class consisting of hy drogen and hydrocarbyl radicalswhich are free of olefini and acetylenic unsaturation and which containfrom to 11 carbon atoms, and Y is selected from the clas consisting ofalkyl and haloalkyl radicals of from 1 to 1 carbon atoms.

A class of aromatic trivalent phosphorus chloride which are particularlysuited for the present purpos are the aromatic dihydrocarbylphosphorochloridites, i.e. compounds of the formula i in which Ar is anaromatic hydrocarbyl radical which is free of olefinic and acetylenicunsaturation and which contains from 6 to 12 carbon atoms. Suchcompounds may be diary-l, bis(alkaryl), bis(aralkyl), aryl alkaryl, arylaralkyl, or alkaryl aralkyl phosphorochloridites, e.g., diphenyl,di-p-tolyl, di-uor fi-naphthyl, dibiphenylyl, dimesityl, dicumyl,bis(2-'butylphenyl), phenyl a-naphthy-l, biphenylyl phenyl,4-ethylphenyl phenyl, debenzyl, bis(2- ethylphenyl) benzyl phenyl,biphenylyl 4-ethylbenzyl, 3- phenylpropyl mesityl, or fi-naphthylmethylphenyl phosphorocloridite.

The corresponding aromatic dihydrocarbyl phosphorochloridodithioites,i.e., compounds of the formula wherein Ar is as defined above, aresimilarly valuable for the present purpose. Such compounds are, forexample, diphenyl phosphorochloridodithioite, dibenzylphosphorochloridodithioite, di-fl-naphthyl phosphorochloridodithioite,biphenylyl phenyl phosphorochloridodithioite, benzyl a-naphthylmethylphosphorochloridodithioite, p-tolyl 2-phenylethyliphosphorochloridodithioite, etc.

Presently useful trivalent phosphorus halides also in- 3,014,950Patented Dec. 26, 1961 clude the O-hydrocarbyl S-hydrocarbylphosphorochloridothioites, i.e., compounds of the formula ArSPCl whereinAr is as above described. Such compounds are, for example, O,S-diphenyl,O-benzyl S-phenyl, O,S-di-finaphthyl, O,S dibenzyl, O,S-di-m-tolyl,O-4-butylpheny-l S-biphenylyl, O-fi-naphthylmethyl S-phenyl, or O-2-phenylethyl S-p-curnyl phosphorochloridothioites.

A very valuable class of the presently useful chlorides includes thearomatic dihydrocarbylphosphinous chlorides, i.e., compounds of theformula wherein Ar is as above defined. Such compounds are, e.g.,diphenylphosphinous chloride, di-p-tolylphosphinous chloride,dibenzylphosphinous chloride, di-aor B-naphthylphosphinous chloride,(2-ethylphenyl)phenylphosphinous chloride, benzylbiphenylylphosphinouschloride, bis(4-petylphenyl)phosphinous chloride, etc.

Also useful in the reaction with aldehyde and triorgano phosphite andthe aromatic hydrocarbyl hydrocarbylphosphonochloridites andphosphonochloridothioites, i.e., compounds of the formula wherein Ar isas above defined and X denotes -O- or S. Examples of such compounds arephenyl, p-tolyl, benzyl, a-naphthyl, or biphenylylphenylphosphonochloridite, phenyl or 4-ethylphenylbenzylphosphonochloridite, phenyl or B-naphthylo-tolylphosphonochloridite, phenyl or benzylbiphenylylphosphonochloridothioite, phenyl or ptolylphenylphosphonochloridothioite, etc.

The above aromatic dihydrocarbyl phosphorochloridites,dihydrocarbylphosphorochloridodithioites, O-hydrocarbyl S-hydrocarbylphosphorochloridothioites, dihydrocarbylphosphinous chlorides,hydrocarbyl hydrocarbylphosphonochlon'dites and hydrocarbylhydrocarbylphosphonochloridothioites may contain one or more halogensubstituents in either the aromatic ring thereof, at an aliphaticradical which is attached to the aromatic ring, or at both the aromaticring and at said aliphatic residue. Examples of such halogen-substitutedcompounds are Bis(octachlorobiphenylyl) phosphorochloridite orphosphorochloridodithioite.

The presently useful aldehydes are formaldehyde and the hydrocarbonaldehydes which are free of olefinic and acetylenic unsaturation. Theyinclude, in addition, to formaldehyde, the alkanecarboxaldehydes such asacetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde,valeraldehyde, isovaleraldehyde, n-hexaldehyde, n-heptaldehyde,2-ethylhexaldehyde, n-octaldehyde, branched-chain nonanal derived by theOxo" process, either n-decanal or branched-chain decanal derived by thex0 process, n-undecanal, and lauraldehyde; the benzenoid aldehydes suchas benzaldehyde, 0-, mor p-tolualdehyde, phenylacetaldehyde,2-phenylpropionaldehyde, 4 ethylphenylacetaldehyde, n-hexylbenzaldehyde,biphenylcarboxaldehyde, and (1- or fl-naphthaldehyde; and thecycloparafiinic aldehydes, such as cyclohexanecarboxaldehyde or 2methylcyclopentanecarboxaldehyde, etc.

Triorgano phosphites useful for the present purpose are the simpletrialkyl phosphites, such as trimethyl, triethyl, triisopropyl,tri-n-butyl, triamyl, tri(2-ethylhexyl), tridecyl, or tridodecylphosphite; the mixed trialkyl phosphites such as dimethyl ethyl, diamylpropyl, ethyl methyl propyl, or dodecyl dimethyl phosphite; the simplehaloalkyl phosphites, such as tris(2 chloroethyl), tris(3- bromopropyl)tris(dichlorooctyl) and tris(3 bromo 2- chloropropyl) phosphite; themixed haloalkyl phosphites,

such as 2-chloroethyl bis(S-bromopropyl) phosphite or 2-chloroethyl4-bromobutyl 2-chloropropyl phosphite; and mixed phosphites of bothparatfinic and haloparafiinic alcohols such as bis(Z-chloroethyl) methylphosphite or 2-chloropropyl diethyl phosphite.

When there is employed as the aromatic trivalent phosphorus halide anaromatic dihydrocarbyl (or halogen-substituted aromatic hydrocarbyl)phosphorochloridite, the products have the formula where R and R arearomatic hydrocarbon radicals which are free of olefinic and acetylenicunsaturation and which contain from 6 to 12 carbon atoms or suchhydrocarbon radicals carrying halogen substitution, Z is selected fromthe class of hydrogen and hydrocarbyl radicals which are free ofolefinic and acetylenic unsaturation and which contain from 1 to 11carbon atoms and Y is an alkyl or haloalkyl radical of from 1 to 12carbon atoms, i.e., the compounds are dihydrocarbyl,bis(halohydrocarbyl) or hydrocarbyl halohydrocarbyl phosphites of alkylor bis (haloalkyl) (l-hydroxyhydrocarbyl) phosphonates.

When the trivalent phosphorus halide is an aromatic dihydrocarbyl oraromatic halogen-substituted dihydrocarbyl phosphorochloridodithioite,the products have the formula II /P-0--('JHP(OY); R'S 2 wherein R, R, Zand Y are as defined above, i.e., the compounds are S,S-dihydrocarbyl,S,S-bis(halohydrocarbyl), S-hydrocarbyl S-halohydrocarbylphosphorodithioites of dialkyl or bis(haloalkyl) (l-hydroxyhydrocarbyl)phosphonates.

Similarly, when the phosphorus halide is an aromatic O-hydrocarbylS-hydrocarbyl phosphorochloridothioite, the products have the formulawherein R, R, Z and Y are as herein defined, i.e., they areO-hydrocarbyl S-hydrocarbyl phosphorothioites of dialkyl orbis(haloalkyl) (l-hydroxyhydrocarbyl)phos phonates or compounds in whicheither both or one of the O-hydrocarbyl and S-hydrocarbyl radicalscontain halogen substitution.

When the aromatic trivalent phosphorus halide is adihydrocarbylphoshinous chloride or a halogen-substituteddihydrocarbylphosphinous chloride, the products aredihydrocarbylphosphinites, bis(halohydrocarbyl)phosphinites, or(halohydrocarbyl)hydrocarbylphosphinites of di- 4 alkyl orbis(haloalkyl) (1 hydroxyhydrocarbyDphosphonates, i.e., they have theformula \P-0CHP(OY): i

wherein R, R, Z and Y are as defined above.

When the aromatic trivalent phosphorus halide is a hydrocarbylhydrocarbylphosphonochloridite or a halogen-substitution productthereof, the presently provided compounds have the formula which isprovided by the present invention is the diphenyl phosphite of diethyl(hydroxymethyl)phosphonate, i.e., lit is a compound in which R and R ofthe above formula are each phenyl radicals, Z is hydrogen, and Y is theethyl radical. It is prepared from diphenyl phosphorochloridite,formaldehyde and triethyl phosphite. A particularly useful compound ofthe above formula is the bis(4-chlorophenyl) phosphite ofbis(Z-chloroethyl) (ahydroxybenzyhphosphonate, i.e., a compound of theabove formula in which R and R are 4-chlorophenyl radicals, Z is thephenyl radical, and Y is the 2-chloroethyl radical. It is prepared frombis(4-chlorophenyl) phosphorochloridite, benzaldehyde and tris(2chloroethyl)phosphite. Other compounds of this formula provided by theinvention are for example:

Diphenyl phosphite of diethyl (1-hydroxyethyl)phosphonate Diphenylphosphite of bis(2-ethy1hexyl) (l-hydroxy- 2-ethylhexyl)phosphonateBis(4-chlorophenyl) phosphite of bis(Z-chloroethyl)(a-hydroxybenzyl)phosphonate Di-a-naphthyl phosphite of di-n-butyl(l-hydroxypropyl)phosphonate Dibiphenylyl phosphite of dimethyl(l-hydroxybutyl) phosphonate Bis(2-ethylphenyl) phosphite of didecyl('l-hydroxyethyl)phosphonate Bis(pentachlorophenyl) phosphite ofbranched-chain dinonyl l-hydroxy-Z-methylpropyl)phosphonate Dibenzylphosphite of dimethyl (l-hydroxydodecyD- phosphonate Bis(4-iodobenzyl)phosphite of diisopropyl (l-hydroxy- 75 hexyl)phosphonate Di-ptolylphosphite of bis(2-chloropropyl) [hydroxy (u-naphthyl)methyl1phosphonateBis(2-bromo-4-ethylphenyl) phosphite of diethyl (1-hydroxyethyDphosphonate Diphenyl phosphite of diisobutyl(cyclohexylhydroxymethyDphQsphonaIte Bis(octachlorobiphenylyl) phosphiteof bis(2-chloroethyl (l-hydroxybenzyl)phosphonate Bis[4-(trichloromethyl)phenyl]phosphite of diethyl1-hydroxyethyl)phosphonate 4-chlorophenyl phenyl phosphite ofbis(trichloroethyl) (a-hydroxybenzyl)phosphonate An example of a usefulcompound of the formula R'S i provided by the invention is theS,S-diphenyl phosphorodithioite of diethyl (hydroxymethyl)phosphonate,i.e., it is a compound in which R and R are phenyl radicals, Z ishydrogen and both Ys are ethyl radicals. It is prepared according to theinvention from diphenyl phosphorochloridodithioite, formaldehyde andtriethyl phosphite. Another compound of the above formula whic isprovided by the invention is the S-u-naphthyl S-pheny phosphorodithioiteof bis(2-chloropropyl) (1- hydroxy ethyl) phosphonate, i.e., it is acompound in which R of the above formula is the a-naphthyl radical, R isthe phenyl radical, Z is the methyl radical and both Y's are2-chloropropyl radicals. It is prepared from a-naphthy phenylphosphorochloridoditlnoite, acetaldehyde and tris (2chloropropyl)phosphite. Other compounds of the above formula provided by theinvention are conveniently set forth in the table below:

R and R= Z= Y= I phenyl ethyl methyl 2-bron1 ophenyl n-bntyl n-butylpentachlorophenyl phenyl 2-chloroethyl benzyl 2-ethylpenty1 dodeeyl2-phenylethyl methyl n-hexyl p-tol nonyl 2-fiuoroethyl fl-naphthyl2-methylpropyl n-octyl biphenylyl ethyl ethyl 4-iodophenyl a-naphthyl2-iodoethyl 2,4-dichlorobenzyl methyl decyl 4-(trifluoromethyl)phenylethyl n-propyl octechlorobiphenylyl phenyl methyl Compounds of theformula P-o--CHi (Y)1 I R z provided by the invention, are, e.g., thediphenylphosphinite of diethyl (hydroxymethyl)phosphonate which isobtained from diphenyl-phosphinous chloride, formaldehyde and triethylphosphite; the di-p-tolylphosphinite of 6 bis(2-ethylhexyl)(1-hydroxypropyl)phosphonate which is obtained fromdi-p-tolylphosphinous chloride, propionaldehyde and tris(2-ethylhexyl)phosphite; the (4-chlorophenyl)-u-naphthylphosphinite ofbis(2-chloroethyl) (ozhydroxybenzyl)phosphonate which is obtained from(4- chlorophenyl-a-naphthyl)phosphinous chloride, bcnzaldehyde andtris(2-chloroethyl) phosphite; and the dibenzylphosphinite of didodecyl(a-naphthylhydroxymethyl) phosphonate which is obtained fromdibenzylphosphinous chloride, a-naphthaldehyde and tridodecyl phosphite.

Examples of compounds of the formula I RO-P-O-OH-h-(O YM provided by theinvention are the phenyl p-chlorophenylphosphonite of dimethyl(hydroxymethyl)phosphonate which is obtained from phenylp-chlorophenylphosphonochloridite, formaldehyde and trimethyl phosphite;the benzyl fi-naphthylphosphonite of bis(2-fluoroethyl) (a-hy.droxy-2-phenylethyl)phosphonate which is prepared from benzylB-naphthylphosphonochloridite, phenylacetadehyde and tris(2-fluoroethyl)phosphite; and the 3,4,5-trichlorophenyl 4-n-butylphenylphosphonite ofbis(2-butylootyl) (l-hydroxypropyl)phosphonate which is prepared from3,4,5-trichlorophenyl 4-n-butylphenylphosphonochloridite,propionaldehyde and tris(2-butylocty1) phosphite.

Compounds of the formula provided by the invention are e.g., the S-pbromophenyl phenylphosphonothioite of diisopropyl (hydroxymethyl)-phosphonate which is prepared from p-bromophenylphenylphosphonochloridothioite, formaldehyde and triisopropyl phosphite;the S-benzyl biphenylylphosphonothioite of bis(2-chloroethyl)(u-hydroxybenzyDphosphonate which is prepared from benzylbiphenylylphosphonochloridothioitc, benzaldehyde and tn's(2-chloroethyl)phosphite; and the S-cumyl B-naphthylphosphonothioite of di-n-hexyl(l-hydroxybutyl)phosphonate which is prepared from cumylfl-naphthylphosphonothioite, butyraldehyde and tri-n-hexyl phosphite.

Reaction of the aromatic trivalent phosphorus chloride, the aldehyde andthe trialkyl or tris(haloalkyl) phosphite takes place readily bycontacting the three reactants at ordinary or moderately increasedtemperatures and allowing the resulting reaction mixture to stand untilformation of the phosphite-phosphonates. Thus, said phosphorus chloridemay be mixed with the phosphite and the aldehyde added to the resultingmixture, or the aldehyde and the phosphite may first be mixed and thechloride added thereto. Because the reaction is generally exothermic,gradual contact of the reactants is :generally rec:- ommended in orderto obtain smooth reaction. However, as will be apparent to those skilledin the art, the exothermal nature of the reaction becomes less of afactor as the molecular weight of the reactants, and particularly of thephosphite, increases. 'It is thus recommended that in each initial run,the three reactants be added to each other gradually at low temperaturesand that external heating be employed only when there appears to be nospontaneous increase in temperature as a consequence of the addition. Inmost instances, the reaction is mildly exothermic initially. Whether thereaction goes to completion without the use of extraneous heat isdetermined by the nature of the reactants. Completion of the reaction,in any event, can be readily ascertained by noting cessation in changeof viscosity, refractive index or the quantity of by-product alkylhalide. Reaction of the three components takes place readily in theabsence of an inert diluent or catalyst. However, catalysts and diluentsor solvents may be employed. The use of diluents may be particularlyadvantageous when working with the more reactive aldehydes; suchdiluents may be, e.g., benzene, toluene, dioxane, methylene chloride orhexane. When employing no diluent and using substantially thestoichiometric proportion of reactants, i.e., one molar equivalent ofthe halogen-containing phosphorus compound, one molar equivalent of thetrivalent phosphorus ester and one molar equivalent of the carbonylcompound, the reaction product may be used directly for a variety ofindustrial and agricultural purposes without purification, i.e., itconsists essentially of the phosphite-phosphonate dissolved in thehaloalkane which is produced as a byproduct in the reaction. Suchsolutions may be used without further purification, e.g., as biologicaltoxicants or gasoline additives. However, the phosphite-phosphonate isreadily separated from the by-product and/or extraneous solvents, e.g.,by distillation. If an excess of any one of the three reactants isinitially present, such an excess may also be separated from the productby distillation.

The presently provided phosphite-phosphonates are stable, generallyhigh-boiling, materials which range from viscid liquids to waxy orcrystalline solids. They are advantageously used as biologicaltoxicants, e.g., as insecticides, fungicides, nematocides andbacteriostats. The essentially aromatic materials, i.e., those obtainedfrom the aromatic trivalent phosphorus chloride and an aromatic aldehydeare particularly useful as functional fluids, e.g., inforce-transmission media. When a plurality of chlorine substituents arepresent at the aromatic ring of said chloride, the compounds are highlyvaluable in dielectric evaluations. The present compounds are generallyuseful as plasticizers for synthetic resins and plastics, asrubber-compounding chemicals and as flameproofing agents for cellulosicand carbonaceous, combustible materials, and as additives to leadedgasolines for the purpose of suppressing pre-ignition glow.

The invention is further illustrated by, but not limited to, thefollowing examples:

Example 1 To a mixture consisting of 59.9 g. (0.36 mole) of triethylphosphite and 91.0 g. (0.36 mole) of diphenyl phosphorochloridite, therewas added, dropwise, 21.0 g. (0.36 mole) of propionaldehyde. Thetemperature rose exothermally to 38 C., at which point ice-cooling wasapplied and the remainder of the aldehyde was added while maintainingthe temperature at from 25 C. When all of the aldehyde had been added,the reaction mixture was heated to 70 C. in order to insure completereaction. By-product ethyl chloride and any unreacted material wereremoved by placing the reaction mixture under water-pump vacuum andheating it to 100 C. Concentration to a pot temperature of 176 C./0.2mm., gave as residue 139.5 g. (94% theoretical yield) of thesubstantially pure diphenyl phosphite of diethyl(1-hydroxypropyl)phosphonate, n 1.5222, analyzing 55.00% carbon and6.48% hydrogen, as against 55.39% and 6.36%, the calculated values, andhaving the structure CsHs-O P O CHP (O CrHs)! Example 2 Acetaldehyde(21.2 g., 0.48 mole) was added, dropwise, to a mixture consisting of121.1 g. (0.45 mole) of tris(2-chloroethyl) phosphite and 108.8 g. (0.43mole) of diphenyl phosphorochloridite. During addition of the aldehyde,the temperature was maintained, by ice-cooling, at from 21-23 C. Whenall of the aldehyde had been added, stirring was continued, first withcooling and subsequently at room temperature, until cessation intemperature rise. The reaction mixture was then heated to C. in order toinsure complete reaction, placed under waterpump vacuum and heated to C.in order to remove by-product 1,2-dichloroethane and any unreactedmaterial, and finally concentrated to 170 C./ 0.6 mm. There was thusobtained as residue 210.4 g. of the substantially pure diphenylphosphite of bis(2-chloroethyl) (l-hydroxyethyl)-phosphonate, 11 1.5351,of the following structure ll (CsH5O)2P 0 (IIHP (O CHaCHnCl):

Example 3 Diphenyl phosphorochloridite (78.2 g., 0.31 mole) was added,dropwise, to a mixture consisting of 132.9 g. (0.31 mole) oftris(2-ethylhexyl) phosphite and 29.2 g. (0.31 mole) of benzaldehyde.During addition of the chloridite, the temperature of the reactionmixture rose spontaneously to 35 C., at which point cooling was appliedand the remainder of the chloridite was added at a temperature of 27-35C. The reaction mixture was then stirred without external cooling untilcessation in emperature rise. The reaction was completed by heating toC., and by-product 2-ethylhexyl chloride and any unreacted material wasremoved by subjecting the mixture to water-pump vacuum and heating it toC. Concentration to C./ 1.0 mm., gave as residue g. (-100% theoreticalyield) of the substantially pure diphenyl phosphite of bis(Z-ethylhexyl)(a-hydroxybenzyl)phosphonate, n 1.5150, analyzing 65.26% carbon and8.11% hydrogen as against 66.91% and 8.01%, the calculated values, andhaving the structure Example 4 Triethyl phosphite (26.6 g., 0.16 mole)was added to a solution of 49.5 g. (0.14 mole) of bis(p-chlorophenyl)phosphorochloridodithioite in75 ml. of benzene. To the resulting mixturethere was gradually added, with cooling, 11.6 g. (0.2 mole) ofpropionaldehyde. The temperature of the reaction mixture during theaddition of the aldehyde was maintained at from 18 C. to 35 C. When allof the aldehyde had been added, the mixture was warmed to 44 C. and anadditional 5 g. portion of the propionaldehyde was added. This caused arapid rise to 47 C. The reaction mixture was then refluxed (68-75 C.)for 0.5 hour, cooled to 25 C., and concentrated to a pot temperature of105 C./0.1 mm., to give 75.1 g. (theory, 71.8 g.) of the substantiallypure bis(S-p-chlorophenyl) phosphorodithioite of diethyl (1-hydroxypropyl)phosphonate, analyzing 14.23% Cl and 11.66% S as against13.8% and 12.5%, the calculated values for C H Cl O P S and having theformula CHQCH;

Example 5 To an ice-cooled mixture consisting of 22.1 g. (0.10 mole) ofdiphenylphosphinous chloride and 16.6 g. (0.10 mole) of triethylphosphite there was added, during 6 minutes, 7.0 g. (0.12 mole) ofpropionaldehyde. Heat of reaction was evidenced during the addition, andwhen cooling was discontinued, the reaction temperature rosespontaneously to 33 C. The colorless reaction mixture was warmed to 65C. and then concentrated to a pot 9 10 temperature of 82 C./0.05 mm., togive 37.5 g. (99% 2. A compound of the formula theoretical yield) of thesubstantially pure diphenylphoshinite of di th 1 1-h drox re 1 ho hon tof the I! structure 6 y y yp py )1 p a e am).

5 R-0 z wherein R and R are aromatic hydrocarbon radicals which are freeof olefinic and acetylenic unsaturation and 11mm which contain from 6 to12 carbon atoms, Z is an alkyl The present compound analyzed as follows:radical of from 1 to 11 carbon atoms and alkyl denotes an alkyl radicalof from 1 to 12 carbon atoms. Found Calcd for 3. A compound of theformula CmHziOiP: R

P 0 CH i 0 1k 1 Pergentc 59.07 6 .0 a y), Percent H 7.03 6.9 15 z inwhich R and R are aromatic hydrocarbon radicals What I claim 1s:

which are free of olefinic and acetylenic unsaturation and A compound ofthe formula which contain from 6 to 12 carbon atoms, Z is an aryl Rradical of from 6 to 11 carbon atoms and alkyl denotes d 0 an alkylradical of from 1 to 12 carbon atoms.

1 4. Diphenyl phosphite of diethyl (l-hydroxypropyh- R (X) P"O"(IJH P(OY) phosphonate.

z 5. Diphenyl phosphite of bis(2-chloroethyl)(l-hydroxyethyDphosphonate. wherein R and R are selected from the classconsisting of (1) aromatic hydrocarbon radicals which are free of g ggzi g gggi figg of blsa'ethylhexyl) olefinic and acetylenic unsaturationand which contain irom 6 to 12 carbon atoms and (2) said aromatichydro-f carbon radicals carrying halogen as substitution, X is selectedfrom the class consisting of --O and S-, n is an integer of 0 to 1, Z isselected from the class consisting of hydrogen, alkyl, aryl, alkaryl andaralkyl radr- References Cited in the file of this Patent cals of from 1to 11 carbon atoms, and Y is selected from the class consisting of alkyland haloalkyl radicals et Bum Akad; w Chemof from 1 to 12 carbon atoms35 $61., 1955, 761-767. (Copy 1n Div. 63.) 260/461.303.

7. Bis(S-p-chlorophenyl) phosphorodithioite of diethyl1hydroxypropyl)phosphonate.

8. Diphenylphosphinite of diethyl (1-hydroxypropyl)- phosphonate.

UNITED STATES PATENT OFFICE CERTIFICATE, OF CORRECTION Patent 03,O14|95O 1 December 26, 1961 Gail H. Birum It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 1, line 55, for "debenzyl" read dibenzyl column 2, llne 22, forVbis(4pety1phenyl)" read bis(dpentylphenyl) Signed and sealed this 11thday of September 1962 (SEAL) Attest:

ERNEST W. SWIDER AVUDL.LADD

UNITED STATES PATENT OFFICE CERTIFICATEv OF CORRECTION Patent No.3,014,950

Gail H. Birum December 26 196 1 It is hereby certified that errorappears in the above numbered patent requiring correction and that thesaid Letters Patent should read as corrected below.

C0lumn 1, line 55,- for "debenzyl" read dibenzyl column 2, line 22, forbis(4petylphenyl)" read bis(4 pentylphenyl) (SEAL) Attest:

ERNEST W. SWIDER Attesting Officer DAVID L. LADD' Commissioner ofPatents UNITED STATES PATENT OFFICE CERTIFICATE, OF CORRECTION PatentNo. 3,014,950 December 26, 196 1 Gail H. Birum It is hereby certifiedthat error appears in the above numbered patent requiring correction andthat the said Letters Patent should read as corrected below.

C0lumn l, line 55 for "debenzyl" read dibenzyl column 2, llne 22, forhis(hpetylphenyl)" read 1015(4- pentylphenyl) Signed and sealed this11th day of; September 1962.

(SEAL) Attest:

ERNEST w. SWIDER DAVID LADD Attesting Officer Commissioner of Patents

1. A COMPOUND OF THE FORMULA